Enzyme Bioelectrochemistry in Cast Biomembrane-Like Films
Enzyme Bioelectrochemistry in Cast Biomembrane-Like Films
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DOI：
10.1002/chin.199834325
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发表时间：
1998-05
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影响因子：
--
通讯作者：
J. Rusling
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文献类型：
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作者：
J. Rusling
对酶电化学的研究部分是由于希望在生物传感器和其他生物医学设备的电极上采用可重复使用的催化涂层。 1-3 同时，电化学方法正在成为研究蛋白质氧化还原化学的重要工具。 4, 5 如果可以实现直接电子交换，电极可以替代酶的氧化还原伙伴。然后，反应的驱动力通过施加的电池电势受到电子控制。扩散在超薄膜中通常并不重要，数据分析被简化，并且只需要少量的酶。酶反应的动力学可以从伏安数据估计。 5g, 6 此外，光学技术与电化学相结合可以表征分子特性。 7 从历史上看，有几个因素一直困扰着电极和蛋白质之间的直接电子转移。图 4a、b 这些包括 (i) 蛋白质结构深处的电活性辅基，(ii) 蛋白质在电极上的吸附变性，以及 (iii) 电极上的不利方向。最近的显着进展提供了几种实现电极和蛋白质之间直接电子交换的策略。除少数例外，需要 8 种特殊的电极制剂。一种方法采用高度纯化的蛋白质溶液和专门清洁的电极。 9 另一种方法是在电极上涂上促进剂分子，促进剂分子通过阻止吸附变性和有利地定向蛋白质来促进电子转移。 4a、b 一种新的变体在金上使用化学吸附的链烷硫醇单层，其末端官能团能够结合蛋白质。 10, 11 同样，具有羧酸盐功能的边缘平面热解石墨电极 (PG) 可以吸附蛋白质。 4c 此外，氧化还原活性水凝胶可用于在电极和酶之间传递电子。 12
Research on the electrochemistry of enzymes is driven partly by the desire to employ reusable catalytic coatings on electrodes for biosensors and other biomedical devices. 1-3 Simultaneously, electrochemical methods are emerging as valuable tools to study protein redox chemistry. 4, 5 If direct electron exchange can be achieved, electrodes can substitute for enzyme redox partners. The driving force of the reaction is then under electronic control via the applied cell potential. Diffusion is often not important in ultrathin films, data analysis is simplified, and only tiny amounts of enzyme are needed. The kinetics of enzymic reactions can be estimated from voltammetric data. 5g, 6 Moreover, optical techniques coupled with electrochemistry can characterize molecular properties. 7 Historically, several factors have plagued direct electron transfer between electrodes and proteins. 4a, b These include (i) electroactive prosthetic groups deep within the protein structure,(ii) adsorptive denaturation of proteins onto electrodes, and (iii) unfavorable orientations at electrodes. Remarkable recent progress provides several strategies for achieving direct electron exchange between electrodes and proteins. With few exceptions, 8 special electrode preparations are required. One approach employs highly purified protein solutions and specially cleaned electrodes. 9 Another coats electrodes with promoter molecules which facilitate electron transfer by blocking adsorptive denaturation and favorably orienting the protein. 4a, b A novel variant uses chemisorbed alkanethiol monolayers on gold, with end functional groups capable of binding proteins. 10, 11 Similarly, edge plane pyrolytic graphite electrodes (PG) with carboxylate functionality can adsorb proteins. 4c Also, redox active hydrogels can be used to deliver electrons between the electrode and enzyme. 12